Thiophene azo carboxylate dyes and laundry care compositions containing the same

ABSTRACT

This application relates to thiophene azo carboxylate dyes for use as hueing agents, laundry care compositions comprising such dyes that may serve as hueing agents, processes for making such dyes and laundry care compositions and methods of using the same. The aforementioned dyes contain a formally charged moiety and are generally comprised of at least two components: at least one chromophore component and at least one polymeric component. Suitable chromophore components generally fluoresce blue, red, violet, or purple color when exposed to ultraviolet light, or they may absorb light to reflect these same shades. Such dyes are advantageous in providing a hueing effect, for example, a whitening effect to fabrics, while not building up over time and causing undesirable blue discoloration to the treated fabrics. Such dyes are also generally stable to bleaching agents used in laundry care compositions.

TECHNICAL FIELD

This application relates to thiophene azo carboxylate dyes for use ashueing agents, laundry care compositions comprising such dyes, processesfor making such dyes and laundry care compositions and methods of usingthe same. The aforementioned dyes contain a formally charged moiety andare generally comprised of at least two components: at least onechromophore component and at least one polymeric component. Suitablechromophore components generally fluoresce blue, red, violet, or purplecolor when exposed to ultraviolet light, or they may absorb light toreflect these same shades. These dyes are advantageous in providing ahueing effect, for example, a whitening effect to fabrics, while notbuilding up over time and causing undesirable discoloration to thetreated fabrics. Such dyes are also generally stable to bleaching agentsused in laundry care compositions.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. Thus, the purpose of hueing agents is generallyto visually brighten these textile substrates and counteract the fadingand yellowing of the substrates. Typically, hueing agents may be foundin laundry detergents, fabric softeners, or rinse aids and are thereforeapplied to textile substrates during the laundering process. However, itis important that hueing agents function to visually brighten treatedtextile substrates without causing undesirable staining of the textilesubstrates. Cellulosic substrates, in particular, tend to exhibit ayellow hue after exposure to light, air, and/or soiling. This yellownessis often difficult to reverse by normal laundering procedures. As aresult, there exists a need for improved hueing agents which are capableof eliminating the yellowness exhibited by ageing cellulosic substrates.By utilizing such improved hueing agents, the life of the textilesubstrates, such as clothing articles, table linens, etc., may beextended. Unfortunately, current thiophene azo dyes, are not asphysically stable as desired. Thus, they require specialsolvents/handling which can limit liquid dye product and laundry carecomposition formulation flexibility. In addition, current thiophene azocarboxylate dyes disclosed for use in laundry compositions, either donot provide the desired hueing benefit at the levels that can be used inproducts, are too costly and/or they build up to an undesirable level,thus overhueing the treated situs over multiple treatment cycles.

The thiophene azo carboxylate dyes disclosed herein and the laundry carecompositions comprising same offer advantages over previous efforts inthis area, as, unlike previous thiophene azo hueing agents, the presentthiophene azo carboxylate dyes comprise a formally charged carboxylatemoiety (above its pKa) that allows such dyes to provide enhanceddeposition, removal and hue angle, without the negatives of pretreatspot staining on polyurea fibers such as Lycra® and/or excessive cost.While not being bound by theory, Applicants believe that such negativesare avoided as the instant thiophene azo carboxylate dyes interacts withmetal ions, for example, in the wash water in a more favorable manner.The aforementioned benefits are offered over a range of fabric types. Inshort, Applicants recognized the source of the current hueingdeficiencies and herein provide the solution to such problem. The hueingcompounds disclosed herein also absorb light at a wavelength appropriateto visually neutralize the yellowness of substrates, including textilesubstrates. These compounds function ideally as hueing agents forsubstrates, including textile substrates, and may be incorporated intolaundry care compositions for use by consumers.

SUMMARY OF INVENTION

This application relates to thiophene azo carboxylate dyes for use ashueing agents, laundry care compositions comprising such dyes that mayserve as hueing agents, processes for making such dyes and laundry carecompositions and methods of using the same. The aforementioned dyescontain a formally charged moiety and are generally comprised of atleast two components: at least one chromophore component and at leastone polymeric component. Suitable chromophore components generallyfluoresce blue, red, violet, or purple color when exposed to ultravioletlight, or they may absorb light to reflect these same shades. Such dyesare advantageous in providing a hueing effect, for example, a whiteningeffect to fabrics, while not building up over time and causingundesirable blue discoloration to the treated fabrics. Such dyes arealso generally stable to bleaching agents used in laundry carecompositions.

DETAILED DESCRIPTION

As used herein, the term “alkoxy” is intended to include C₁-C₈ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the terms “alkyl” and “alkyl capped” are intended toinclude C₁-C₁₈ alkyl groups, and in one aspect, C₁-C₆ alkyl groups.

As used herein, the term “aryl” is intended to include C₃-C₁₂ arylgroups.

As used herein, the term “arylalkyl” is intended to include C₁-C₁₈ alkylgroups and, in one aspect, C₁-C₆ alkyl groups.

As used herein, the term “formally charged moiety” means a moiety havingat least one formal positive charge or at least one formal negativecharge in aqueous solution at a pH in the range from 7 to 11.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose barform and/or flake type washing agents and/or fabric treatmentcompositions.

As used herein, the term “fabric treatment composition” includes, unlessotherwise indicated, fabric softening compositions, fabric enhancingcompositions, fabric freshening compositions and combinations there of.Such compositions may be, but need not be rinse added compositions.

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, the articles including “the”, “a” and “an” when used ina claim, are understood to mean one or more of what is claimed ordescribed.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

As used herein, the term “maximum extinction coefficient” is intended todescribe the molar extinction coefficient at the maximum wavelength inthe range of 400 nanometers to 750 nanometers.

As a consequence of their manufacturing process, the thiophene azocarboxylate dyes disclosed herein may contain a distribution ofrepeating units in their polymeric moiety. Accordingly, in one aspect,the molecular weight of the thiophene azo carboxylate dyes disclosedherein may be reported as an average molecular weight, as determined byits molecular weight distribution.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

Laundry Care Composition Comprising Suitable Hueing Agents

In one aspect, a laundry care composition comprising a hueing agent andone or more laundry care ingredients is disclosed. Suitable hueingagents include all the hueing agents listed below.

In one aspect, a composition comprising a thiophene azo carboxylate dyecontaining a carboxylic acid moiety, with the proviso that the thiopheneazo carboxylate dye does not have the following structures

is disclosed.

b) a laundry care ingredient.

In one aspect of the laundry care composition, said thiophene azocarboxylate dye has, in the wavelength range of about 400 nm to about750 nm in methanol solution, a maximum extinction coefficient greaterthan about 1000 liter/mol/cm.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye has, in the wavelength range of about 540nm to about 630 nm, a maximum extinction coefficient from about 20,000to about 100,000 liter/mol/cm.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye has, in the wavelength range of about 560nm to about 610 nm, a maximum extinction coefficient from about 20,000to about 65,000 liter/mol/cm.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye has a molecular weight from greater than232 Daltons, from about 233 Daltons to about 5000 Daltons, from about365 Daltons to about 2500 Daltons, or even from about 423 Daltons toabout 1000 Daltons.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye is represented by general Formula (I):

wherein:

-   -   a.) R₁, R₂ and R₃ are each independently selected from hydrogen,        electron-withdrawing moieties, and electron-donating moieties,        provided that at least one of R₁, R₂ and R₃ is an        electron-withdrawing moiety; and    -   b.) wherein X is an organic moiety having a molecular weight        from about 104 Daltons to about 4871 Daltons, from about 236        Daltons to about 2371 Daltons from about 294 Daltons to about        871 Daltons.

In one aspect of the aforementioned laundry care composition, for saidthiophene azo carboxylate dye having Formula I, each R₁, R₂ and R₃ isindependently selected from hydrogen, (C₁-C₄)-alkyl, (C₃-C₁₀)-aryl,carboxylate, cyano, sulfonate, phosphonate, sulfate, acetate, nitro,(C₁-C₄)-alkyl ester, halogen or amino moiety.

In one aspect of the aforementioned laundry care composition, for saidthiophene azo carboxylate dye having Formula I, X is a moiety havingFormula (II) below:

wherein:

-   -   i.) R₄ is selected from a moiety having Formula (III) below

-   -   -   wherein:            -   each R₈ is independently selected from hydrogen, C₁-C₈                alkyl optionally substituted with a hydroxy, or acetyl;            -   m is an integer from 0 to 10;            -   Y is —OC(O)GCO₂M wherein M is H or a charge balancing                cation; G is an organic group derived from a substituted                or unsubstituted succinic, maleic, glutaric, adipic or                phthalic anhydride having Formula IV,

-   -   -   -   said anhydride having a molecular weight less than about                353 Daltons, from about 98 Daltons to 352 Daltons, or                even from about 100 Daltons to about 325 Daltons;

    -   ii) R₄ is selected from a moiety having Formula (V) below:

-   -   -   wherein            -   each R₁₁ and R₁₂ is independently selected from                hydrogen, C₁-C₈ alkyl, aryl, acetyl or hydroxyl moiety;                m and n are independent and are integers from 0 to 10,            -   Y is —OC(O)GCO₂M wherein M is H or a charge balancing                cation; G is an organic group derived from a substituted                or unsubstituted succinic, maleic, glutaric, adipic or                phthalic anhydride having Formula VI,

-   -   -   -   said anhydride having a molecular weight less than about                353 Daltons, from about 98 Daltons to 352 Daltons, or                even from about 100 Daltons to about 325 Daltons; or

    -   iii.) R₄ is selected from a moiety having Formula (VII) below:

-   -   -   wherein            -   R₁₃ is selected from a C₆-C₁₀ aryl moiety, C₇-C₁₂                arylalkyl moiety, C₁-C₁₈ alkyl moiety, or a siloxane                moiety;            -   each R₁₄ is independently selected from hydrogen, C₁-C₄                alkyl; m is an integer from 0 to 10;            -   Y is —OC(O)GCO₂M wherein M is H or a charge balancing                cation; G is an organic group derived from a substituted                or unsubstituted succinic, maleic, glutaric, adipic or                phthalic anhydride having Formula VIII,

-   -   -   -   said anhydride having a molecular weight less than about                353 Daltons, from about 98 Daltons to 352 Daltons, or                even from about 100 Daltons to about 325 Daltons;

    -   R₅ is an independently selected R₄ moiety as defined above or R₅        is selected from C₁-C₁₂ alkyl moiety, a C₂-C₁₂ ether moiety;        C₆-C₁₀ aryl moiety or C₇-C₁₂ arylalkyl moiety; wherein the index        a is an integer from 0 to 4, and each R₆ may be independently        selected from a C₁-C₆ alkyl, a C₁-C₄ alkoxy, a nitro, a        hydroxyl, a halogen, or —NHC(O)R₂₂ wherein R₂₂ is selected from        H, —NH₂, C₁-C₆ alkyl, phenyl, —(CH₂)_(s)OR₂₃ where the index s        is 1 or 2 and R₂₃ is selected from Me, phenyl, and —CO₂CH₂CN;        —NHSO₂R₂₄ wherein R₂₄ is C₁-C₄ alkyl or phenyl; said alkyl,        alkoxy and acetamido moieties may be optionally substituted with        a carboxylate moiety;

or, X is a moiety having Formula II above:

wherein each R4 and R5 can independently be selected from:

a) [(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)R₁₅];

b) C₁-C₁₂ alkyl, C₆-C₁₀ aryl or C₇-C₁₂ aryl alkyl;

c) [CH₂CH(OR₁₆)CH₂OR₁₇];

d) the amino addition product of styrene oxide, glycidyl methyl ether,isobutyl glycidyl ether, isopropylglycidyl ether, t-butyl glycidylether, 2-ethylhexylgycidyl ether, and glycidylhexadecyl ether, followedby the addition of from 1 to 10 alkylene oxide units wherein at leastone such alkyleneoxide unit is substituted with R₁₅ that is not —H;wherein R′ is selected from the group consisting of H, CH₃,CH₂O(CH₂CH₂O)_(z)R₁₅, and mixtures thereof; R″ is selected from thegroup consisting of H, CH₂O(CH₂CH₂O)_(z)R₁₅, and mixtures thereof;x+y≦20; y≧1; z=0 to 10; each R₁₅ is independently selected from —H and Ywherein Y is —OC(O)GCO₂M wherein M is H or a charge balancing cation; Gis an organic group derived from a substituted or unsubstitutedsuccinic, maleic, glutaric, adipic or phthalic anhydride having FormulaIX,

-   -   said anhydride having a molecular weight less than about 353        Daltons, from about 98 Daltons to 352 Daltons, or even from        about 100 Daltons to about 325 Daltons;    -   R₁₆ is selected from the group consisting of H, (CH₂CH₂O)_(z)R₁₅        wherein z=0 to 10, and mixtures thereof; R₁₇ is selected from        the group consisting of C₁-C₁₆ alkyl, C₆-C₁₀ aryl groups, and        mixtures thereof; the index m is an integer from 0 to 4 and each        R₆ is as defined above; further provided the molecule contains        at least one non-H R₁₅ group.

In one aspect of the aforementioned laundry care composition, for saidthiophene azo carboxylate dye having Formula I X is a moiety havingFormula (II) below:

wherein:

-   -   i.) R₄ is selected from a moiety having Formula (III) below

-   -   -   wherein:            -   R₈ is a hydrogen, C₁-C₄ alkyl moiety or an C₆-C₁₀ aryl                moiety;            -   Y is —OC(O)GCO₂M wherein M is H or a charge balancing                cation; G is an organic group derived from a substituted                or unsubstituted succinic, maleic, glutaric, adipic or                phthalic anhydride having Formula IV,

-   -   -   -   said anhydride having a molecular weight less than about                353 Daltons, from about 98 Daltons to 352 Daltons, or                even from about 100 Daltons to about 325 Daltons;

        -   or, R₄ is selected from a moiety having Formula (V) below:

-   -   -   wherein            -   each R₁₁ and R₁₂ is independently selected from                hydrogen, C₁-C₄ alkyl or C₆-C₁₀ aryl moiety; m and n are                independent and are integers from 0 to 5,            -   Y is —OC(O)GCO₂M wherein M is H or a charge balancing                cation; G is an organic group derived from a substituted                or unsubstituted succinic, maleic, glutaric, adipic or                phthalic anhydride having Formula VI,

-   -   -   -   said anhydride having a molecular weight less than about                353 Daltons, from about 98 Daltons to 352 Daltons, or                even from about 100 Daltons to about 325 Daltons;

        -   or, R₄ is selected from a moiety having Formula (VII) below:

-   -   -   wherein            -   R₁₃ is selected from an C₆-C₁₀ aryl moiety, benzyl                moiety, or a C₁-C₁₈ alkyl moiety;            -   each R₁₄ is independently selected from hydrogen or                —CH₃;            -   m is an integer from 0 to 10,            -   Y is —OC(O)GCO₂M wherein M is H or a charge balancing                cation; G is an organic group derived from a substituted                or unsubstituted succinic, maleic, glutaric, adipic or                phthalic anhydride having Formula VIII,

-   -   -   -   said anhydride having a molecular weight less than about                353 Daltons, from about 98 Daltons to 352 Daltons, or                even from about 100 Daltons to about 325 Daltons;

    -   ii.) R₅ is an independently selected R₄ moiety as defined above        or R₅ is R₅ selected from C₁-C₆ alkyl moiety or benzyl moiety;

    -   iii.) wherein the index a is an integer from 0 to 2, and each R₆        may be independently selected from methyl, methoxy, or acetamido        moiety.

In one aspect of the aforementioned laundry care composition, for saidthiophene azo carboxylate dye having Formula I, each R₁, R₂ and R₃ isindependently selected from hydrogen, (C₁-C₄)-alkyl, (C₆-C₁₀)-aryl,carboxylate, cyano, sulfonate, acetate, nitro, (C₁-C₄)-alkyl ester,halogen or amino moiety, in one aspect, each R₁, R₂ and R₃ isindependently selected from hydrogen, (C₁-C₄)-alkyl, carboxylate, cyano,sulfonate, nitro, (C₁-C₄)-alkyl ester or halogen moiety.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye has Formula (X):

A-N═N—X  Formula X

wherein the A moiety is selected from the group consisting of Table 1 AMoieties Nos. 1-118 and wherein X is selected from the group consistingof Table 4 X Moieties Nos. 1-24 wherein G is an organic group derivedfrom a substituted or unsubstituted succinic, maleic, glutaric, adipicor phthalic anhydride having Formula XI,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye has Formula (XII):

A-N═N—X  Formula XII

wherein the A moiety is selected from the group consisting of Table 1 AMoieties Nos. 9-11, 15, 23, 34-35, 37-39, 41, 43, 47, 50-51, 57-58, 77,83, 89, 95, 106, and 110-118; and wherein the X moiety is selected fromthe group consisting of Table 4 X Moieties Nos. 1-8, 13, 14, and 18-21,wherein G is an organic group derived from a substituted orunsubstituted succinic, maleic, glutaric, adipic or phthalic anhydridehaving Formula XIII,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons. In one aspect of the aforementioned laundry carecomposition, said G moiety of said thiophene azo carboxylate dye isselected from Table 5 G Moieties Nos. 1-48.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye has the following formula:

wherein the moiety A is selected from Table 1 A Moieties Nos. 1-118; a=0to 2; when a=1 or 2, R₆ is selected from Table 2 R₆ Substituent Identityand Position Nos. 1-40; and R₄ and R₅ grouping is selected from Table 3R₄ and R₅ Groupings Nos. 1-83.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye has the following formula:

wherein the moiety A is selected from Table 1 A Moieties Nos. 9-11, 15,23, 34-35, 37-39, 41, 43, 47, 50-51, 57-58, 77, 83, 89, 95, 106, and110-118; a=0 to 2; when a=1 or 2, R₆ is selected from Table 2 R₆Substituent Identity and Position Nos. 1, 3, 5, 7, 12, 13, 14, 31, 36and 40; and R₄ and R₅ grouping is selected from Table 3 R₄ and R₅Groupings Nos. 3-8, 14, 15, 18-23, 29, 30, 33-38, 44, 45, 48-53, 59, 60,63-66, 71-76, 82 and 83.

In one aspect of the aforementioned laundry care composition, saidthiophene azo carboxylate dye has a formula selected from Table 6Formula Nos. 1-48, in one aspect, said thiophene azo carboxylate dye hasa formula selected from Table 6 Formula Nos. 1-36, 43 and 44.

A moieties may be selected from the moieties shown in Table 1:

TABLE 1 A Moieties No. A 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

87

88

89

90

91

92

93

94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

111

112

113

114

115

116

117

118

R₆ may be selected from the substituents shown in Table 2:

TABLE 2 R₆ Substituent-Identity and Position

R₆ Substituent -Identity and Position on Aniline Ring No. 1 2 3 4 1 —OH2 —Cl —OH 3 —OMe —OH 4 —On-Bu —OH 5 —Me 6 —Me —Me 7 —OMe —Me 8 —OEt —Me9 —Cl 10 —Br 11 —NO₂ 12 —NH₂ 13 —NHAc 14 —OMe —NHAc 15 —NHC(O)Et 16 —OMe—NHC(O)Et 17 —OEt —NHC(O)Et 18 —NHC(O)n-Pr 19 —Me —NHC(O)n-Pr 20—NHC(O)i-Pr 21 —NHC(O)n-Bu 22 —OMe —NHC(O)n-Bu 23 —NHC(O)c-C₆H₁₁ 24—NHC(O)Ph 25 —OMe —NHC(O)Ph 26 —NHC(O)CH₂OMe 27 —NHC(O)CH₂OPh 28—NHC(O)CH₂CH₂OMe 29 —NHC(O)CH₂CH₂OEt 30 —NHC(O)(CH₂)₂CO₂CH₂CN 31—NHC(O)NH₂ 32 —NHSO₂Me 33 —NHSO₂Et 34 —OMe —NHSO₂Et 35 —NHSO₂Ph 36 —OMe37 —Me 38 —Cl 39 —NO₂ 40 —OMe —OMe

R₄ and R₅ groupings may be selected from the groupings shown in Table 3:

TABLE 3 R₄ and R₅ Groupings R₄ and R₅ Groupings No. R₄ R₅ 1 Ethyl

2 Ethyl

3 Ethyl

4 Ethyl

5 Ethyl

6 Ethyl

7 Ethyl

8 Ethyl

9 Ethyl

10 Ethyl

11 Ethyl

12 Ethyl

13 Ethyl

14 Ethyl

15 Ethyl

16 Benzyl

17 Benzyl

18 Benzyl

19 Benzyl

20 Benzyl

21 Benzyl

22 Benzyl

23 Benzyl

24 Benzyl

25 Benzyl

26 Benzyl

27 Benzyl

28 Benzyl

29 Benzyl

30 Benzyl

31 Hexyl

32 Hexyl

33 Hexyl

34 Hexyl

35 Hexyl

36 Hexyl

37 Hexyl

38 Hexyl

39 Hexyl

40 Hexyl

41 Hexyl

42 Hexyl

43 Hexyl

44 Hexyl

45 Hexyl

46 Isopropyl

47 Isopropyl

48 Isopropyl

49 Isopropyl

50 Isopropyl

51 Isopropyl

52 Isopropyl

53 Isopropyl

54 Isopropyl

55 Isopropyl

56 Isopropyl

57 Isopropyl

58 Isopropyl

59 Isopropyl

60 Isopropyl

61

62

63

64

65

66

67

68

69 Methoxyethyl

70 Methoxyethyl

71 Methoxyethyl

72 Methoxyethyl

73 Methoxyethyl

74 Methoxyethyl

75 Methoxyethyl

76 Methoxyethyl

77 Methoxyethyl

78 Methoxyethyl

79 Methoxyethyl

80 Methoxyethyl

81 Methoxyethyl

82 Methoxyethyl

83 Methoxyethyl

The “*” denotes point of attachment to additional moieties. “M” denotesH or the appropriate charge balancing counterion.

X moieties may be selected from the moieties shown in Table 4:

TABLE 4 X Moieties No. G moieties may be selected from moieties 1-48shown in Table 5. 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

The “*” denotes point of attachment to the azo moiety.

G moieties in the X moieties in Table 4 above may be selected frommoieties 1-48 shown in Table 5:

TABLE 5 G Moieties No. G moiety 1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

Anhydrides suitable for use in creating the Y moiety in the instantinvention include, but are not limited to, the following:3-(2E)-2-dodecen-1-yldihydro-2,5-Furandione;(3aR,7aS)-rel-3a,4,7,7a-tetrahydro-4,7-Epoxyisobenzofuran-1,3-dione;3-hexyldihydro-3-methyl-2,5-Furandione; 3-hexyldihydro-2,5-Furandione;(3aR,8aS)-rel-hexahydro-1H-Cyclohepta[c]furan-1,3(3aH)-dione;(3aR,6aS)-rel-tetrahydro-1H-Cyclopenta[c]furan-1,3(3aH)-dione;5-(1,1-dimethylethyl)-1,3-Isobenzofurandione;dihydro-3-(phenylmethyl)-2,5-Furandione; 3-decyldihydro-2,5-Furandione;dihydro-3,3-dimethyl-2,5-Furandione;(3aR,4S,7R,7aS)-rel-hexahydro-4,7-Methanoisobenzofuran-1,3-dione;3-ethyldihydro-2,5-Furandione;(3aR,7aS)-rel-3a,4,7,7a-tetrahydro-5,6-dimethyl-1,3-Isobenzofurandione;3-(2-hexen-1-yl)dihydro-2,5-Furandione;dihydro-3-(2-propen-1-yl)-2,5-Furandione;hexahydro-4,7-Methanoisobenzofuran-1,3-dione;5,6-dimethyl-1,3-Isobenzofurandione;tetrahydro-1H-Cyclopenta[c]furan-1,3(3aH)-dione;5-nitro-1,3-Isobenzofurandione;hexahydro-4,7-Epoxyisobenzofuran-1,3-dione;3a,4,7,7a-tetrahydro-4,7-Epoxyisobenzofuran-1,3-dione;5,6-dimethoxy-1,3-Isobenzofurandione; dihydro-3-octyl-2,5-Furandione;dihydro-3-methyl-2,5-Furandione;1,3-dihydro-1,3-dioxo-5-Isobenzofurancarboxylic acid, methyl ester;3-dodecyldihydro-2,5-Furandione; dihydro-3-phenyl-2,5-Furandione;3a,4,7,7a-tetrahydro-4,7-Methanoisobenzofuran-1,3-dione;4-nitro-1,3-Isobenzofurandione;1,3-dihydro-1,3-dioxo-5-Isobenzofurancarboxylic acid;(3aR,4S,7R,7aS)-rel-3a,4,7,7a-tetrahydro-4,7-Methanoisobenzofuran-1,3-dione;4,5,6,7-tetrachloro-1,3-Isobenzofurandione; dihydro-2,5-Furandione;1,3-Isobenzofurandione; 3a,4,7,7a-tetrahydro-1,3-Isobenzofurandione;hexahydro-1,3-Isobenzofurandione;(3aR,4S,7R,7aS)-rel-hexahydro-3a,7a-dimethyl-4,7-Epoxyisobenzofuran-1,3-dione;4-hexyldihydro-2H-Pyran-2,6(3H)-dione;dihydro-4-(2-methylpropyl)-2H-Pyran-2,6(3H)-dione;4-[[(1,1-dimethylethyl)dimethylsilyl]oxy]dihydro-2H-Pyran-2,6(3H)-dione;4,4-dimethyl-1H-2-Benzopyran-1,3(4H)-dione;4-ethyldihydro-4-methyl-2H-Pyran-2,6(3H)-dione;8-Oxaspiro[4.5]decane-7,9-dione;dihydro-4,4-dimethyl-2H-Pyran-2,6(3H)-dione;dihydro-3-phenyl-2H-Pyran-2,6(3H)-dione;dihydro-3,3-dimethyl-2H-Pyran-2,6(3H)-dione;1H-2-Benzopyran-1,3(4H)-dione; dihydro-2H-Pyran-2,6(3H)-dione;1H,3H-Naphtho[1,8-cd]pyran-1,3-dione;3-Oxabicyclo[3.2.1]octane-2,4-dione; Dibenz[c,e]oxepin-5,7-dione;4,5-dihydro-2-Benzoxepin-1,3-dione; and 2,7-Oxepanedione. Such suitableanhydrides may be obtained from one or more of the following: 3BScientific Corporation, Libertyville, Ill., 60048; Accel Pharmtech, LLC,East Brunswick, N.J., 08816; A Chemtek, Worcester, Mass., 01606; AKScientific, Inc., Union City, Calif., 94587; AKos Consulting andSolutions Deutschland GmbH, Steinen, D-79585, Germany; Alfa Aesar, WardHill, Mass., 01835; Allichem LLC, Baltimore, Md., 21224; American CustomChemicals Corp., San Diego, Calif., 92196-2527; Aurora Fine ChemicalsLLC, San Diego, Calif., 92126; Beta Pharma Scientific, Inc., Branford,Conn., 06405; City Chemical LLC, West Haven, Conn., 06516; RyanScientific, Inc., Mt. Pleasant, S.C., 29465; Sigma-Aldrich, St. Louis,Mo., 63178; TCI America, Portland, Oreg., 97203; Waterstone Technology,Carmel, Ind., 46032; and Youchemicals Limited, Minhang, Shanghai,201100, People's Republic of China.

It is contemplated to be within the scope of this invention that thethiophene azo carboxylate dye may comprise any one of the A moietiesselected from Table 1, any one of the R₆ substituents selected fromTable 2, any one of the R₄ and R₅ groupings selected from Table 3, anyone of the X moieties selected from Table 4, and any one of the Gmoieties selected from Table 5.

In yet another aspect of the invention, suitable thiophene azocarboxylate dyes include, but are not limited to, the structures shownin Table 6:

TABLE 6 Thiophene Azo Carboxylate Dyes No. Formula Example  1

Example  2

Example  3

Example  4

Example  5

Example  6

Example  7

Example  8

Example  9

Example 10

Example 11

Example 12

Example 13

Example 14

Example 15

Example 16

Example 17

Example 18

Example 19

Example 20

Example 21

Example 22

Example 23

Example 24

Example 25

Example 26

Example 27

Example 28

Example 29

Example 30

Example 31

Example 32

Example 33

Example 34

Example 35

Example 36

Example 37

Example 38

Example 39

Example 40

Example 41

Example 42

Example 43

Example 44

Example 45

Example 46

Example 47

Example 48

As indicated previously, the hueing agents described in the presentspecification may be incorporated into laundry care compositionsincluding but not limited to laundry detergents and fabric carecompositions. The laundry care compositions including laundry detergentsmay be in solid or liquid form, including a gel form, and/or unit doesforms, including multi-compartment unit dose forms. Such compositionsmay comprise one or more of said hueing agents and a laundry careingredient.

In one aspect, said laundry care composition may comprise, based ontotal laundry care composition weight, less than 15% builder, less than10% builder, or even less than 5% builder.

In one aspect, said laundry care composition may comprise, based ontotal laundry care composition weight, a total of no more than 20%water; a total of no more than 15% water; a total of no more than 10%water; or even a total of no more than 5% water.

In one aspect, said laundry care composition may comprise, based ontotal laundry care composition weight, from about 10% to about 70% of awater-miscible organic solvent having a molecular weight of greater than70 Daltons.

In one aspect, said laundry care composition may comprise, based ontotal laundry care composition weight, a perfume microcapsule comprisinga core and a shell that encapsulates said core, said perfumemicrocapsule having a D[4,3] average particle of from about 0.01 micronsto about 200 microns and optionally a formaldehyde scavenger that issupplied via the addition of the microcapsules (contained in a perfumemicrocapsule slurry that is added to the laundry care ingredient) and/oradded directly to the laundry care composition. In one aspect, the shellof said perfume microcapsules may be made of any material, includingmaterials selected from the group consisting of polyethylenes,polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters,polyacrylates, polyureas, polyurethanes, polyolefins, polysaccharides,epoxy resins, vinyl polymers, and mixtures thereof. In one aspect,useful shell materials include materials that are sufficientlyimpervious to the core material and the materials in the environment inwhich the perfume microcapsule will be employed, to permit the deliveryperfume to be obtained. Suitable impervious shell materials includematerials selected from the group consisting of reaction products of oneor more amines with one or more aldehydes, such as urea cross-linkedwith formaldehyde or gluteraldehyde, melamine cross-linked withformaldehyde; gelatin-polyphosphate coacervates optionally cross-linkedwith gluteraldehyde; gelatin-gum Arabic coacervates; cross-linkedsilicone fluids; polyamine reacted with polyisocyanates and mixturesthereof. In one aspect, the shell material comprises melaminecross-linked with formaldehyde and/or a polyacrylate. Suitable perfumemicrocapsules may be obtained from Appleton Papers of Appleton Wis.,USA.

In one aspect, suitable formaldehyde scavengers include materialsselected from the group consisting of sodium bisulfite, urea, ethyleneurea, cysteine, cysteamine, lysine, glycine, serine, carnosine,histidine, glutathione, 3,4-diaminobenzoic acid, allantoin, glycouril,anthranilic acid, methyl anthranilate, methyl 4-aminobenzoate, ethylacetoacetate, acetoacetamide, malonamide, ascorbic acid,1,3-dihydroxyacetone dimer, biuret, oxamide, benzoguanamine,pyroglutamic acid, pyrogallol, methyl gallate, ethyl gallate, propylgallate, triethanol amine, succinamide, thiabendazole, benzotriazol,triazole, indoline, sulfanilic acid, oxamide, sorbitol, glucose,cellulose, poly(vinyl alcohol), partially hydrolyzedpoly(vinylformamide), poly(vinyl amine), poly(ethylene imine),poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine),poly(4-aminostyrene), poly(l-lysine), chitosan, hexane diol,ethylenediamine-N,N′-bisacetoacetamide, N-(2-ethylhexyl)acetoacetamide,2-benzoylacetoacetamide, N-(3-phenylpropyl)acetoacetamide, lilial,helional, melonal, triplal, 5,5-dimethyl-1,3-cyclohexanedione,2,4-dimethyl-3-cyclohexenecarboxaldehyde,2,2-dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine,triethylenetetramine, ammonium hydroxide, benzylamine,hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione,dehydroacetic acid, or a mixture thereof. These formaldehyde scavengersmay be obtained from Sigma/Aldrich/Fluka of St. Louis, Mo. U.S.A. orPolySciences, Inc. of Warrington, Pa. U.S.A.

Such formaldehyde scavengers are typically combined with a slurrycontaining said perfume microcapsules, at a level, based on total slurryweight, of from about 2 wt. % to about 18 wt. %, from about 3.5 wt. % toabout 14 wt. % or even from about 5 wt. % to about 13 wt. %.

In one aspect, such formaldehyde scavengers may be combined with aproduct containing a perfume microcapsule, said scavengers beingcombined with said product at a level, based on total product weight, offrom about 0.005% to about 0.8%, alternatively from about 0.03% to about0.5%, alternatively from about 0.065% to about 0.25% of the productformulation.

In another aspect, such formaldehyde scavengers may be combined with aslurry containing said perfume microcapsules, at a level, based on totalslurry weight, of from about 2 wt. % to about 14 wt. %, from about 3.5wt. % to about 14 wt. % or even from about 5 wt. % to about 14 wt. % andsaid slurry may be added to a product matrix to which addition anidentical or different scavenger may be added at a level, based on totalproduct weight, of from about 0.005% to about 0.5%, alternatively fromabout 0.01% to about 0.25%, alternatively from about 0.05% to about0.15% of the product formulation.

In one aspect, one or more of the aforementioned formaldehyde scavengersmay be combined with a liquid fabric enhancing product containingperfume microcapsules at a level, based on total liquid fabric enhancingproduct weight, of from 0.005% to about 0.8%, alternatively from about0.03% to about 0.4%, alternatively from about 0.06% to about 0.25% ofthe product formulation.

In one aspect, such formaldehyde scavengers may be combined with aliquid laundry detergent product containing perfume microcapsules, saidscavengers being selected from the group consisting of sodium bisulfite,urea, ethylene urea, cysteine, cysteamine, lysine, glycine, serine,carnosine, histidine, glutathione, 3,4-diaminobenzoic acid, allantoin,glycouril, anthranilic acid, methyl anthranilate, methyl4-aminobenzoate, ethyl acetoacetate, acetoacetamide, malonamide,ascorbic acid, 1,3-dihydroxyacetone dimer, biuret, oxamide,benzoguanamine, pyroglutamic acid, pyrogallol, methyl gallate, ethylgallate, propyl gallate, triethanol amine, succinamide, thiabendazole,benzotriazol, triazole, indoline, sulfanilic acid, oxamide, sorbitol,glucose, cellulose, poly(vinyl alcohol), partially hydrolyzedpoly(vinylformamide), poly(vinyl amine), poly(ethylene imine),poly(oxyalkyleneamine), poly(vinyl alcohol)-co-poly(vinyl amine),poly(4-aminostyrene), poly(l-lysine), chitosan, hexane diol,ethylenediamine-N,N′-bisacetoacetamide, N-(2-ethylhexyl)acetoacetamide,2-benzoylacetoacetamide, N-(3-phenylpropyl)acetoacetamide, lilial,helional, melonal, triplal, 5,5-dimethyl-1,3-cyclohexanedione,2,4-dimethyl-3-cyclohexenecarboxaldehyde,2,2-dimethyl-1,3-dioxan-4,6-dione, 2-pentanone, dibutyl amine,triethylenetetramine, ammonium hydroxide, benzylamine,hydroxycitronellol, cyclohexanone, 2-butanone, pentane dione,dehydroacetic acid and mixtures thereof, and combined with said liquidlaundry detergent product at a level, based on total liquid laundrydetergent product weight, of from about 0.003 wt. % to about 0.20 wt. %,from about 0.03 wt. % to about 0.20 wt. % or even from about 0.06 wt. %to about 0.14 wt. %.

The hueing agents may be added to substrates using a variety ofapplication techniques. For instance, for application tocellulose-containing textile substrates, the hueing agent may beincluded as a component of a laundry detergent. Thus, application to acellulose-containing textile substrate actually occurs when a consumeradds laundry detergent to a washing machine. The hueing agent may bepresent in the laundry detergent composition in an amount from about0.000001% to about 10% by weight of the composition, from about 0.00001%to about 10% by weight of the composition, from about 0.0001% to about5% by weight of the composition, and even from about 0.0001% to about 1%by weight of the composition.

The laundry detergent composition typically comprises a surfactant in anamount sufficient to provide desired cleaning properties. In one aspect,the laundry detergent composition may comprise, based on total laundrydetergent composition weight, from about 0.5% to about 99% of thesurfactant; from about 1% to about 95% of the surfactant; from about 5%to about 90% of the surfactant, from about 5% to about 70% of thesurfactant, or even from about 5% to about 40% of the surfactant. Thesurfactant may comprise anionic, nonionic, cationic, zwitterionic and/oramphoteric surfactants. In one aspect, the detergent compositioncomprises anionic surfactant, nonionic surfactant, or mixtures thereof.

Fabric care compositions are typically added in the rinse cycle, whichis after the detergent solution has been used and replaced with therinsing solution in typical laundering processes. The fabric carecompositions disclosed herein may be comprise a rinse added fabricsoftening active and a suitable hueing agent as disclosed in the presentspecification. The fabric care composition may comprise, based on totalfabric care composition weight, from about 1% to about 90%, or fromabout 5% to about 50% fabric softening active. The hueing agent may bepresent in the fabric care composition in an amount from about 0.5 ppbto about 50 ppm, or from about 0.5 ppm to about 30 ppm.

Suitable Laundry Care Ingredients

While not essential for the purposes of the present invention, thenon-limiting list of laundry care ingredients illustrated hereinafterare suitable for use in the laundry care compositions and may bedesirably incorporated in certain aspects of the invention, for exampleto assist or enhance performance, for treatment of the substrate to becleaned, or to modify the aesthetics of the composition as is the casewith perfumes, colorants, dyes or the like. It is understood that suchingredients are in addition to the components that were previouslylisted for any particular aspect. The total amount of such adjuncts mayrange, once the amount of dye is taken into consideration from about 90%to about 99.99999995% by weight of the laundry care composition.

The precise nature of these additional components, and levels ofincorporation thereof, will depend on the physical form of thecomposition and the nature of the operation for which it is to be used.Suitable laundry care ingredients include, but are not limited to,fabric softening actives, polymers, for example cationic polymers,surfactants, builders, chelating agents, dye transfer inhibiting agents,dispersants, enzymes, and enzyme stabilizers, catalytic materials,bleach activators, polymeric dispersing agents, clay soilremoval/anti-redeposition agents, brighteners, suds suppressors, dyes,perfume(s) including quadrant perfumes and additional perfume deliverysystems including perfume loaded zeolites, starch encapsuled accords,and Schiff base pro-perfumes, structure elasticizing agents, fabricsofteners, carriers, hydrotropes, processing aids and/or pigments. Inaddition to the disclosure below, suitable examples of such otheradjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282,6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

As stated, the laundry care ingredients are not essential to Applicants'laundry care compositions. Thus, certain aspects of Applicants'compositions do not contain one or more of the following adjunctsmaterials: fabric softening actives, bleach activators, surfactants,builders, chelating agents, dye transfer inhibiting agents, dispersants,enzymes, and enzyme stabilizers, catalytic metal complexes, polymericdispersing agents, clay and soil removal/anti-redeposition agents,brighteners, suds suppressors, dyes, additional perfumes and perfumedelivery systems, structure elasticizing agents, fabric softeners,carriers, hydrotropes, processing aids and/or pigments. However, whenone or more adjuncts are present, such one or more adjuncts may bepresent as detailed below:

Surfactants

Suitable anionic surfactants useful herein can comprise any of theconventional anionic surfactant types typically used in liquid detergentproducts. These include the alkyl benzene sulfonic acids and their saltsas well as alkoxylated or non-alkoxylated alkyl sulfate materials.

Exemplary anionic surfactants are the alkali metal salts of C₁₀-C₁₆alkyl benzene sulfonic acids, or C₁₁-C₁₄ alkyl benzene sulfonic acids.In one aspect, the alkyl group is linear and such linear alkyl benzenesulfonates are known as “LAS”. Alkyl benzene sulfonates, andparticularly LAS, are well known in the art. Such surfactants and theirpreparation are described for example in U.S. Pat. Nos. 2,220,099 and2,477,383. Especially useful are the sodium and potassium linearstraight chain alkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about 11 to 14. Sodium C₁₁-C₁₄,e.g., C₁₂, LAS is a specific example of such surfactants.

Another exemplary type of anionic surfactant comprises ethoxylated alkylsulfate surfactants. Such materials, also known as alkyl ether sulfatesor alkyl polyethoxylate sulfates, are those which correspond to theformula: R′—O—(C₂H₄O)_(n)—SO₃M wherein R′ is a C₈-C₂₀ alkyl group, n isfrom about 1 to 20, and M is a salt-forming cation. In one aspect, R′ isC₁₀-C₁₈ alkyl, n is from about 1 to 15, and M is sodium, potassium,ammonium, alkylammonium, or alkanolammonium. In one aspect, R′ is aC₁₂-C₁₆, n is from about 1 to 6 and M is sodium.

The alkyl ether sulfates will generally be used in the form of mixturescomprising varying R′ chain lengths and varying degrees of ethoxylation.Frequently such mixtures will inevitably also contain somenon-ethoxylated alkyl sulfate materials, i.e., surfactants of the aboveethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkylsulfates may also be added separately to the compositions of thisinvention and used as or in any anionic surfactant component which maybe present. Specific examples of non-alkoxylated, e.g., non-ethoxylated,alkyl ether sulfate surfactants are those produced by the sulfation ofhigher C₈-C₂₀ fatty alcohols. Conventional primary alkyl sulfatesurfactants have the general formula: ROSO₃-M⁺ wherein R is typically alinear C₈-C₂₀ hydrocarbyl group, which may be straight chain or branchedchain, and M is a water-solubilizing cation. In one aspect, R is aC₁₀-C₁₅ alkyl, and M is alkali metal, more specifically R is C₁₂-C₁₄ andM is sodium.

Specific, non-limiting examples of anionic surfactants useful hereininclude: a) C₁₁-C₁₈ alkyl benzene sulfonates (LAS); b) C₁₀-C₂₀ primary,branched-chain and random alkyl sulfates (AS); c) C₁₀-C₁₈ secondary(2,3) alkyl sulfates having formulae (I) and (II): wherein M in formulae(I) and (II) is hydrogen or a cation which provides charge neutrality,and all M units, whether associated with a surfactant or adjunctingredient, can either be a hydrogen atom or a cation depending upon theform isolated by the artisan or the relative pH of the system whereinthe compound is used, with non-limiting examples of suitable cationsincluding sodium, potassium, ammonium, and mixtures thereof, and x is aninteger of at least about 7, or at least about 9, and y is an integer ofat least 8, or at least about 9; d) C₁₀-C₁₈ alkyl alkoxy sulfates(AE_(x)S) wherein x is from 1-30; e) C₁₀-C₁₈ alkyl alkoxy carboxylatesin one aspect, comprising 1-5 ethoxy units; f) mid-chain branched alkylsulfates as discussed in U.S. Pat. No. 6,020,303 and U.S. Pat. No.6,060,443; g) mid-chain branched alkyl alkoxy sulfates as discussed inU.S. Pat. No. 6,008,181 and U.S. Pat. No. 6,020,303; h) modifiedalkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242,WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO00/23549, and WO 00/23548; i) methyl ester sulfonate (MES); and j)alpha-olefin sulfonate (AOS).

Suitable nonionic surfactants useful herein can comprise any of theconventional nonionic surfactant types typically used in liquiddetergent products. These include alkoxylated fatty alcohols and amineoxide surfactants. In one aspect, for use in the liquid detergentproducts herein are those nonionic surfactants which are normallyliquid.

Suitable nonionic surfactants for use herein include the alcoholalkoxylate nonionic surfactants. Alcohol alkoxylates are materials whichcorrespond to the general formula: R¹(C_(m)H_(2m)O)_(n)OH wherein R¹ isa C₈-C₁₆ alkyl group, m is from 2 to 4, and n ranges from about 2 to 12.In one aspect, R¹ is an alkyl group, which may be primary or secondary,that comprises from about 9 to 15 carbon atoms, or from about 10 to 14carbon atoms. In one aspect, the alkoxylated fatty alcohols will also beethoxylated materials that contain from about 2 to 12 ethylene oxidemoieties per molecule, or from about 3 to 10 ethylene oxide moieties permolecule.

The alkoxylated fatty alcohol materials useful in the liquid detergentcompositions herein will frequently have a hydrophilic-lipophilicbalance (HLB) which ranges from about 3 to 17 from about 6 to 15, orfrom about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants havebeen marketed under the tradenames Neodol and Dobanol by the ShellChemical Company.

Another suitable type of nonionic surfactant useful herein comprises theamine oxide surfactants. Amine oxides are materials which are oftenreferred to in the art as “semi-polar” nonionics. Amine oxides have theformula: R(EO)_(x)(PO)_(y)(BO)_(z)N(O)(CH₂R)₂.qH₂O. In this formula, Ris a relatively long-chain hydrocarbyl moiety which can be saturated orunsaturated, linear or branched, and can contain from 8 to 20, 10 to 16carbon atoms, or is a C₁₂-C₁₆ primary alkyl. R′ is a short-chain moiety,in one aspect R′ may be selected from hydrogen, methyl and —CH₂OH. Whenx+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy andBO is butyleneoxy. Amine oxide surfactants are illustrated by C₁₂₋₁₄alkyldimethyl amine oxide.

Non-limiting examples of nonionic surfactants include: a) C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; b) C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; c) C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block polymerssuch as Pluronic® from BASF; d) C₁₄-C₂₂ mid-chain branched alcohols, BA,as discussed in U.S. Pat. No. 6,150,322; e) C₁₄-C₂₂ mid-chain branchedalkyl alkoxylates, BAE_(x), wherein x if from 1-30, as discussed in U.S.Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,093,856;f) Alkylpolysaccharides as discussed in U.S. Pat. No. 4,565,647 toLlenado, issued Jan. 26, 1986; specifically alkylpolyglycosides asdiscussed in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; g)Polyhydroxy fatty acid amides as discussed in U.S. Pat. No. 5,332,528,WO 92/06162, WO 93/19146, WO 93/19038, and WO 94/09099; and h) ethercapped poly(oxyalkylated) alcohol surfactants as discussed in U.S. Pat.No. 6,482,994 and WO 01/42408.

In the laundry detergent compositions herein, the detersive surfactantcomponent may comprise combinations of anionic and nonionic surfactantmaterials. When this is the case, the weight ratio of anionic tononionic will typically range from 10:90 to 90:10, more typically from30:70 to 70:30.

Cationic surfactants are well known in the art and non-limiting examplesof these include quaternary ammonium surfactants, which can have up to26 carbon atoms. Additional examples include a) alkoxylate quaternaryammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; b)dimethyl hydroxyethyl quaternary ammonium as discussed in U.S. Pat. No.6,004,922; c) polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d)cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660, 4,260,529 and U.S. Pat. No. 6,022,844; and e) aminosurfactants as discussed in U.S. Pat. No. 6,221,825 and WO 00/47708,specifically amido propyldimethyl amine (APA).

Non-limiting examples of zwitterionic surfactants include derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 throughcolumn 22, line 48, for examples of zwitterionic surfactants; betaine,including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine,C₈ to C₁₈ (in one aspect C₁₂ to C₁₈) amine oxides and sulfo and hydroxybetaines, such as N-alkyl-N,N-dimethylamino-1-propane sulfonate wherethe alkyl group can be C₈ to C₁₈, or C₁₀ to C₁₄.

Non-limiting examples of ampholytic surfactants include aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents comprises at least about 8 carbon atoms, typically fromabout 8 to about 18 carbon atoms, and at least one comprises an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column19, lines 18-35, for examples of ampholytic surfactants.

Aqueous, Non-Surface Active Liquid Carrier

As noted, the laundry care compositions may be in the form of a solid,either in tablet or particulate form, including, but not limited toparticles, flakes, sheets, or the like, or the compositions may be inthe form of a liquid. The liquid detergent compositions may comprise anaqueous, non-surface active liquid carrier. Generally, the amount of theaqueous, non-surface active liquid carrier employed in the compositionsherein will be effective to solubilize, suspend or disperse thecomposition components. For example, the liquid detergent compositionsmay comprise, based on total liquid detergent composition weight, fromabout 5% to about 90%, from about 10% to about 70%, or from about 20% toabout 70% of the aqueous, non-surface active liquid carrier.

The most cost effective type of aqueous, non-surface active liquidcarrier is typically water. Accordingly, the aqueous, non-surface activeliquid carrier component will generally be mostly, if not completely,comprised of water. While other types of water-miscible liquids, suchalkanols, diols, other polyols, ethers, amines, and the like, have beenconventionally been added to liquid detergent compositions asco-solvents or stabilizers, for purposes of the present invention, theutilization of such water-miscible liquids typically is minimized tohold down composition cost. Accordingly, the aqueous liquid carriercomponent of the liquid detergent products herein will generallycomprise water present in concentrations ranging from about 5% to about90%, or from about 5% to about 70%, by weight of the liquid detergentcomposition.

Bleaching Agents

Bleaching Agents—The cleaning compositions of the present invention maycomprise one or more bleaching agents. Suitable bleaching agents otherthan bleaching catalysts include photobleaches, bleach activators,hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids andmixtures thereof. In general, when a bleaching agent is used, thecompositions of the present invention may comprise from about 0.1% toabout 50% or even from about 0.1% to about 25% bleaching agent by weightof the subject cleaning composition. Examples of suitable bleachingagents include:

(1) photobleaches for example sulfonated zinc phthalocyanine;

(2) preformed peracids: Suitable preformed peracids include, but are notlimited to, compounds selected from the group consisting ofpercarboxylic acids and salts, percarbonic acids and salts, perimidicacids and salts, peroxymonosulfuric acids and salts, for example,Oxzone®, and mixtures thereof. Suitable percarboxylic acids includehydrophobic and hydrophilic peracids having the formula R—(C═O)O—O-Mwherein R is an alkyl group, optionally branched, having, when theperacid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12carbon atoms and, when the peracid is hydrophilic, less than 6 carbonatoms or even less than 4 carbon atoms; and M is a counterion, forexample, sodium, potassium or hydrogen;

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof. In one aspect ofthe invention the inorganic perhydrate salts are selected from the groupconsisting of sodium salts of perborate, percarbonate and mixturesthereof. When employed, inorganic perhydrate salts are typically presentin amounts of from 0.05 to 40 wt %, or 1 to 30 wt % of the overallcomposition and are typically incorporated into such compositions as acrystalline solid that may be coated. Suitable coatings include,inorganic salts such as alkali metal silicate, carbonate or borate saltsor mixtures thereof, or organic materials such as water-soluble ordispersible polymers, waxes, oils or fatty soaps; and

(4) bleach activators having R—(C═O)-L wherein R is an alkyl group,optionally branched, having, when the bleach activator is hydrophobic,from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when thebleach activator is hydrophilic, less than 6 carbon atoms or even lessthan 4 carbon atoms; and L is leaving group. Examples of suitableleaving groups are benzoic acid and derivatives thereof—especiallybenzene sulphonate. Suitable bleach activators include dodecanoyloxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzenesulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzenesulphonate (NOBS). Suitable bleach activators are also disclosed in WO98/17767. While any suitable bleach activator may be employed, in oneaspect of the invention the subject cleaning composition may compriseNOBS, TAED or mixtures thereof.

When present, the peracid and/or bleach activator is generally presentin the composition in an amount of from about 0.1 to about 60 wt %, fromabout 0.5 to about 40 wt % or even from about 0.6 to about 10 wt % basedon the composition. One or more hydrophobic peracids or precursorsthereof may be used in combination with one or more hydrophilic peracidor precursor thereof.

The amounts of hydrogen peroxide source and peracid or bleach activatormay be selected such that the molar ratio of available oxygen (from theperoxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.

Bleach Boosting Compounds—The compositions herein may comprise one ormore bleach boosting compounds. Bleach boosting compounds provideincreased bleaching effectiveness in lower temperature applications. Thebleach boosters act in conjunction with conventional peroxygen bleachingsources to provide increased bleaching effectiveness. This is normallyaccomplished through in situ formation of an active oxygen transferagent such as a dioxirane, an oxaziridine, or an oxaziridinium.Alternatively, preformed dioxiranes, oxaziridines and oxaziridiniums maybe used.

Among suitable bleach boosting compounds for use in accordance with thepresent invention are cationic imines, zwitterionic imines, anionicimines and/or polyionic imines having a net charge of from about +3 toabout −3, and mixtures thereof. These imine bleach boosting compounds ofthe present invention include those of the general structure:

where R¹-R⁴ may be a hydrogen or an unsubstituted or substituted radicalselected from the group consisting of phenyl, aryl, heterocyclic ring,alkyl and cycloalkyl radicals.

Suitable bleach boosting compounds include zwitterionic bleach boosterszwitterionic bleach boosters, which are described in U.S. Pat. Nos.5,576,282 and 5,718,614. Other bleach boosting compounds includecationic bleach boosters described in U.S. Pat. Nos. 5,360,569;5,442,066; 5,478,357; 5,370,826; 5,482,515; 5,550,256; and WO 95/13351,WO 95/13352, and WO 95/13353.

Peroxygen sources are well-known in the art and the peroxygen sourceemployed in the present invention may comprise any of these well knownsources, including peroxygen compounds as well as compounds, which underconsumer use conditions, provide an effective amount of peroxygen insitu. The peroxygen source may include a hydrogen peroxide source, thein situ formation of a peracid anion through the reaction of a hydrogenperoxide source and a bleach activator, preformed peracid compounds ormixtures of suitable peroxygen sources. Of course, one of ordinary skillin the art will recognize that other sources of peroxygen may beemployed without departing from the scope of the invention. The bleachboosting compounds, when present, are typically employed in conjunctionwith a peroxygen source in the bleaching systems of the presentinvention.

Enzyme Bleaching—Enzymatic systems may be used as bleaching agents. Thehydrogen peroxide may also be present by adding an enzymatic system(i.e. an enzyme and a substrate therefore) which is capable ofgenerating hydrogen peroxide at the beginning or during the washingand/or rinsing process. Such enzymatic systems are disclosed in EPPatent Application 91202655.6 filed Oct. 9, 1991.

The present invention compositions and methods may utilize alternativebleach systems such as ozone, chlorine dioxide and the like. Bleachingwith ozone may be accomplished by introducing ozone-containing gashaving ozone content from about 20 to about 300 g/m³ into the solutionthat is to contact the fabrics. The gas:liquid ratio in the solutionshould be maintained from about 1:2.5 to about 1:6. U.S. Pat. No.5,346,588 describes a process for the utilization of ozone as analternative to conventional bleach systems and is herein incorporated byreference.

In one aspect, the fabric softening active (“FSA”) is a quaternaryammonium compound suitable for softening fabric in a rinse step. In oneaspect, the FSA is formed from a reaction product of a fatty acid and anaminoalcohol obtaining mixtures of mono-, di-, and, in one aspect,triester compounds. In another aspect, the FSA comprises one or moresoftener quaternary ammonium compounds such, but not limited to, as amonoalkyquaternary ammonium compound, a diamido quaternary compound anda diester quaternary ammonium compound, or a combination thereof.

In one aspect of the invention, the FSA comprises a diester quaternaryammonium (hereinafter “DQA”) compound composition. In certain aspects ofthe present invention, the DQA compounds compositions also encompasses adescription of diamido FSAs and FSAs with mixed amido and ester linkagesas well as the aforementioned diester linkages, all herein referred toas DQA.

A first type of DQA (“DQA (1)”) suitable as a FSA in the present CFSCincludes a compound comprising the formula:

{R_(4-m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)}X⁻

wherein each R substituent is either hydrogen, a short chain C₁-C₆, forexample C₁-C₃ alkyl or hydroxyalkyl group, e.g., methyl, ethyl, propyl,hydroxyethyl, and the like, poly (C₂₋₃ alkoxy), for example, polyethoxy,group, benzyl, or mixtures thereof; each m is 2 or 3; each n is from 1to about 4, or 2; each Y is —O—(O)C—, —C(O)—O—, —NR—C(O)—, or —C(O)—NR—and it is acceptable for each Y to be the same or different; the sum ofcarbons in each R¹, plus one when Y is —O—(O)C— or —NR—C(O)—, isC₁₂-C₂₂, or C₁₄-C₂₀, with each R¹ being a hydrocarbyl, or substitutedhydrocarbyl group; it is acceptable for R¹ to be unsaturated orsaturated and branched or linear and in one aspect it is linear; it isacceptable for each R¹ to be the same or different and typically theseare the same; and X⁻ can be any softener-compatible anion, suitableanions include, chloride, bromide, methylsulfate, ethylsulfate, sulfate,phosphate, and nitrate, in one aspect the anions are chloride or methylsulfate. Suitable DQA compounds are typically made by reactingalkanolamines such as MDEA (methyldiethanolamine) and TEA(triethanolamine) with fatty acids. Some materials that typically resultfrom such reactions include N,N-di(acyl-oxyethyl)-N,N-dimethylammoniumchloride or N,N-di(acyl-oxyethyl)-N,N-methylhydroxyethylammoniummethylsulfate wherein the acyl group is derived from animal fats,unsaturated, and polyunsaturated, fatty acids, e.g., tallow, hardendedtallow, oleic acid, and/or partially hydrogenated fatty acids, derivedfrom vegetable oils and/or partially hydrogenated vegetable oils, suchas, canola oil, safflower oil, peanut oil, sunflower oil, corn oil,soybean oil, tall oil, rice bran oil, palm oil, etc.

Non-limiting examples of suitable fatty acids are listed in U.S. Pat.No. 5,759,990 at column 4, lines 45-66. In one aspect, the FSA comprisesother actives in addition to DQA (1) or DQA. In yet another aspect, theFSA comprises only DQA (1) or DQA and is free or essentially free of anyother quaternary ammonium compounds or other actives. In yet anotheraspect, the FSA comprises the precursor amine that is used to producethe DQA.

In another aspect of the invention, the FSA comprises a compound,identified as DTTMAC comprising the formula:

[R_(4-m)—N⁽⁺⁾—R¹ _(m)]A⁻

wherein each m is 2 or 3, each R¹ is a C₆-C₂₂, or C₁₄-C₂₀, but no morethan one being less than about C₁₂ and then the other is at least about16, hydrocarbyl, or substituted hydrocarbyl substituent, for example,C₁₀-C₂₀ alkyl or alkenyl (unsaturated alkyl, including polyunsaturatedalkyl, also referred to sometimes as “alkylene”), in one aspect C₁₂-C₁₈alkyl or alkenyl, and branch or unbranched. In one aspect, the IodineValue (IV) of the FSA is from about 1 to 70; each R is H or a shortchain C₁-C₆, or C₁-C₃ alkyl or hydroxyalkyl group, e.g., methyl, ethyl,propyl, hydroxyethyl, and the like, benzyl, or (R²O)₂₋₄H where each R²is a C₁₋₆ alkylene group; and A⁻ is a softener compatible anion,suitable anions include chloride, bromide, methylsulfate, ethylsulfate,sulfate, phosphate, or nitrate; in one aspect the anions are chloride ormethyl sulfate.

Examples of these FSAs include dialkydimethylammonium salts anddialkylenedimethylammonium salts such as ditallowdimethylammonium andditallowdimethylammonium methylsulfate. Examples of commerciallyavailable dialkylenedimethylammonium salts usable in the presentinvention are di-hydrogenated tallow dimethyl ammonium chloride andditallowdimethyl ammonium chloride available from Degussa under thetrade names Adogen® 442 and Adogen® 470 respectively. In one aspect, theFSA comprises other actives in addition to DTTMAC. In yet anotheraspect, the FSA comprises only compounds of the DTTMAC and is free oressentially free of any other quaternary ammonium compounds or otheractives.

In one aspect, the FSA comprises an FSA described in U.S. Pat. Pub. No.2004/0204337 A1, published Oct. 14, 2004 to Corona et al., fromparagraphs 30-79. In another aspect, the FSA is one described in U.S.Pat. Pub. No. 2004/0229769 A1, published Nov. 18, 2005, to Smith et al.,on paragraphs 26-31; or U.S. Pat. No. 6,494,920, at column 1, line 51 etseq. detailing an “esterquat” or a quaternized fatty acidtriethanolamine ester salt.

In one aspect, the FSA is chosen from at least one of the following:ditallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methylsulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride,dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, orcombinations thereof.

In one aspect, the FSA may also include amide containing compoundcompositions. Examples of diamide comprising compounds may include butnot limited to methyl-bis(tallowamidoethyl)-2-hydroxyethylammoniummethyl sulfate (available from Degussa under the trade names Varisoft110 and Varisoft 222). An example of an amide-ester containing compoundisN-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N-methylamine.

Another aspect of the invention provides for a rinse added fabricsoftening composition further comprising a cationic starch. Cationicstarches are disclosed in US 2004/0204337 A1. In one aspect, the rinseadded fabric softening composition comprises from about 0.1% to about 7%of cationic starch by weight of the fabric softening composition. In oneaspect, the cationic starch is HCP401 from National Starch.

Builders—The compositions of the present invention can comprise one ormore detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder, or fromabout 5% or 10% to about 80%, 50%, or even 30% by weight, of saidbuilder. Builders include, but are not limited to, the alkali metal,ammonium and alkanolammonium salts of polyphosphates, alkali metalsilicates, alkaline earth and alkali metal carbonates, aluminosilicatebuilders polycarboxylate compounds, ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, andcarboxymethyl-oxysuccinic acid, the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylatessuch as mellitic acid, succinic acid, oxydisuccinic acid, polymaleicacid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid,and soluble salts thereof.

Chelating Agents—The compositions herein may also optionally contain oneor more copper, iron and/or manganese chelating agents. If utilized,chelating agents will generally comprise from about 0.1% by weight ofthe compositions herein to about 15%, or even from about 3.0% to about15% by weight of the compositions herein.

Dye Transfer Inhibiting Agents—The compositions of the present inventionmay also include one or more dye transfer inhibiting agents. Suitablepolymeric dye transfer inhibiting agents include, but are not limitedto, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in the compositions herein, the dye transfer inhibiting agentsare present at levels from about 0.0001%, from about 0.01%, from about0.05% by weight of the cleaning compositions to about 10%, about 2%, oreven about 1% by weight of the cleaning compositions.

Dispersants—The compositions of the present invention can also containdispersants. Suitable water-soluble organic materials are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acid maycomprise at least two carboxyl radicals separated from each other by notmore than two carbon atoms.

Enzymes—The compositions can comprise one or more detergent enzymeswhich provide cleaning performance and/or fabric care benefits. Examplesof suitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, keratanases, reductases, oxidases,phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase,chondroitinase, laccase, and amylases, or mixtures thereof. A typicalcombination is a cocktail of conventional applicable enzymes likeprotease, lipase, cutinase and/or cellulase in conjunction with amylase.

Enzyme Stabilizers—Enzymes for use in compositions, for example,detergents can be stabilized by various techniques. The enzymes employedherein can be stabilized by the presence of water-soluble sources ofcalcium and/or magnesium ions in the finished compositions that providesuch ions to the enzymes.

Processes of Making Laundry Care Compositions

The laundry care compositions of the present invention can be formulatedinto any suitable form and prepared by any process chosen by theformulator, non-limiting examples of which are described in Applicants'examples and in U.S. Pat. No. 5,879,584; U.S. Pat. No. 5,691,297; U.S.Pat. No. 5,574,005; U.S. Pat. No. 5,569,645; U.S. Pat. No. 5,565,422;U.S. Pat. No. 5,516,448; U.S. Pat. No. 5,489,392; U.S. Pat. No.5,486,303 all of which are incorporated herein by reference.

The liquid detergent compositions may be in the form of an aqueoussolution or uniform dispersion or suspension of surfactant, hueingagent, and certain optional other ingredients, some of which maynormally be in solid form, that have been combined with the normallyliquid components of the composition, such as the liquid alcoholethoxylate nonionic, the aqueous liquid carrier, and any other normallyliquid optional ingredients. Such a solution, dispersion or suspensionwill be acceptably phase stable and will typically have a viscositywhich ranges from about 100 to 600 cps, or from about 150 to 400 cps.For purposes of this invention, viscosity is measured with a BrookfieldLVDV-II+ viscometer apparatus using a #21 spindle.

The liquid detergent compositions herein can be prepared by combiningthe components thereof in any convenient order and by mixing, e.g.,agitating, the resulting component combination to form a phase stableliquid detergent composition. In a process for preparing suchcompositions, a liquid matrix is formed containing at least a majorproportion, or even substantially all, of the liquid components, e.g.,nonionic surfactant, the non-surface active liquid carriers and otheroptional liquid components, with the liquid components being thoroughlyadmixed by imparting shear agitation to this liquid combination. Forexample, rapid stifling with a mechanical stirrer may usefully beemployed. While shear agitation is maintained, substantially all of anyanionic surfactants and the solid form ingredients can be added.Agitation of the mixture is continued, and if necessary, can beincreased at this point to form a solution or a uniform dispersion ofinsoluble solid phase particulates within the liquid phase. After someor all of the solid-form materials have been added to this agitatedmixture, particles of any enzyme material to be included, e.g., enzymeprills, are incorporated. As a variation of the composition preparationprocedure hereinbefore described, one or more of the solid componentsmay be added to the agitated mixture as a solution or slurry ofparticles premixed with a minor portion of one or more of the liquidcomponents. After addition of all of the composition components,agitation of the mixture is continued for a period of time sufficient toform compositions having the requisite viscosity and phase stabilitycharacteristics. Frequently this will involve agitation for a period offrom about 30 to 60 minutes.

In one aspect of forming the liquid detergent compositions, the hueingagent is first combined with one or more liquid components to form ahueing agent premix, and this hueing agent premix is added to acomposition formulation containing a substantial portion, for examplemore than 50% by weight, more specifically, more than 70% by weight, andyet more specifically, more than 90% by weight, of the balance ofcomponents of the laundry detergent composition. For example, in themethodology described above, both the hueing agent premix and the enzymecomponent are added at a final stage of component additions. In anotheraspect, the hueing agent is encapsulated prior to addition to thedetergent composition, the encapsulated hueing agent is suspended in astructured liquid, and the suspension is added to a compositionformulation containing a substantial portion of the balance ofcomponents of the laundry detergent composition.

As noted previously, the detergent compositions may be in a solid form.Suitable solid forms include tablets and particulate forms, for example,granular particles, flakes or sheets. Various techniques for formingdetergent compositions in such solid forms are well known in the art andmay be used herein. In one aspect, for example when the composition isin the form of a granular particle, the hueing agent is provided inparticulate form, optionally including additional but not all componentsof the laundry detergent composition. The hueing agent particulate iscombined with one or more additional particulates containing a balanceof components of the laundry detergent composition. Further, the hueingagent, optionally including additional but not all components of thelaundry detergent composition, may be provided in an encapsulated form,and the hueing agent encapsulate is combined with particulatescontaining a substantial balance of components of the laundry detergentcomposition.

The compositions of this invention, prepared as hereinbefore described,can be used to form aqueous washing solutions for use in the launderingof fabrics. Generally, an effective amount of such compositions is addedto water, for example in a conventional fabric laundering automaticwashing machine, to form such aqueous laundering solutions. The aqueouswashing solution so formed is then contacted, typically under agitation,with the fabrics to be laundered therewith. An effective amount of theliquid detergent compositions herein added to water to form aqueouslaundering solutions can comprise amounts sufficient to form from about500 to 7,000 ppm of composition in aqueous washing solution, or fromabout 1,000 to 3,000 ppm of the detergent compositions herein will beprovided in aqueous washing solution.

Method of Use

Certain of the consumer products disclosed herein can be used to cleanor treat a situs inter alia a surface or fabric. Typically at least aportion of the situs is contacted with an embodiment of Applicants'consumer product, in neat form or diluted in a liquor, for example, awash liquor and then the situs may be optionally washed and/or rinsed.In one aspect, a situs is optionally washed and/or rinsed, contactedwith an aspect of the consumer product and then optionally washed and/orrinsed. For purposes of the present invention, washing includes but isnot limited to, scrubbing, and mechanical agitation. The fabric maycomprise most any fabric capable of being laundered or treated in normalconsumer use conditions. Liquors that may comprise the disclosedcompositions may have a pH of from about 3 to about 11.5. Suchcompositions are typically employed at concentrations of from about 500ppm to about 15,000 ppm in solution. When the wash solvent is water, thewater temperature typically ranges from about 5° C. to about 90° C. and,when the situs comprises a fabric, the water to fabric ratio istypically from about 1:1 to about 30:1. Employing one or more of theaforementioned methods results in a treated situs.

In one aspect, a method of treating and/or cleaning a surface or fabriccomprising the steps of optionally washing and/or rinsing said surfaceor fabric, contacting said surface or fabric with any laundry carecomposition disclosed in this specification, then optionally washingand/or rinsing said surface and/or fabric then optionally letting saidsurface or fabric to dry and/or actively drying said surface or fabric,is disclosed.

EXAMPLES

The following examples are provided to further illustrate the hueingagents of the present invention; however, they are not to be construedas limiting the invention as defined in the claims appended hereto. Infact, it will be apparent to those skilled in the art that variousmodifications and variations can be made in this invention withoutdeparting from the scope or spirit of the invention. All parts andpercents given in these examples are by weight unless otherwiseindicated.

Sample Preparation and Test Methods A. Sample Preparation

The following general procedures were used to prepare the thiophene azodyes of the present invention.

Preparation of Glycidol Materials

18 parts N-ethyl-m-toluidine, 52 parts isopropyl-glycidyl ether, and 50parts toluene were charged into a 200 mL round bottom flask at roomtemperature. The mixture was refluxed overnight. The solvent was removedand the resulting material was used crude for the next step. Thesematerials were then alkoxylated as described herein.

Preparation of Alkoxylated Intermediates General Procedure forAlkoxylation—Method A:

Intermediate Type 1, Initial Single Site Polymer

18 parts N-ethyl-m-toluidine, 14 parts acetic acid, and 20 parts waterwere charged into a 200 mL stainless steel autoclave at roomtemperature. 11 parts ethylene oxide was added over several hours. Afterthe reaction was kept for 24 hours at room temperature, the vessel wascharged with 0.2 parts NaOH and heated up to 125° C. Then, ethyleneoxide was added over about 1 hour. After continuing the reaction foranother 3 hours at 125° C., residual EO was removed by vacuum. Then itwas cooled to room temperature and the intermediate obtained was anamber-colored viscous liquid. The constant average number of EO could beachieved every time by controlling the amount of ethylene oxide in thesynthesis.

Intermediate Type 2, Initial Dual Chain Polymer

18 parts 2-Methoxy-5-methylaniline, 14 parts acetic acid, and 20 partswater were charged into a 200 mL stainless steel autoclave at roomtemperature. 22 parts ethylene oxide was added over several hours. Afterthe reaction was kept for 24 hours at room temperature, the vessel wascharged with 0.2 parts NaOH and heated up to 125° C. Then, 40 partsethylene oxide was added over about 1 hour. After continuing thereaction for another 3 hours at 125° C., residual EO was removed byvacuum. Then it was cooled to room temperature and the intermediateobtained was an amber-colored viscous liquid. The constant averagenumber of EO could be achieved every time by controlling the amount ofethylene oxide in the synthesis.

General Procedure for Alkoxylation—Method B:

18 parts aniline, 60 parts mono-bromo-polyethylene glycol-200, 20 partsNaHCO₃ and 50 parts toluene were charged into a 200 mL round bottomflask at room temperature. The reaction mixture was heated to 80° C. for5 hours. The salt was filtered and the solvent removed from the filtratevia low pressure distillation. The crude product was used with nofurther purification for the next step.

It is also possible to use a mono-bromo-mono-chloro glycol in order todirectly make the halogenated product using this same procedure above.

General Procedures for Color Synthesis

All colors were prepared following the same general procedure.

Color intermediate synthesis for Example 1

2 parts amino-thiophene, and 30 parts phosphoric acid, were charged into200 mL glass flask and cooled to 0-5° C. 1 part NaNO₂ was slowly addedas a solid, maintaining the temperature below 10° C. When addition wascompleted for diazotization, the mixture was stirred for 30 minutes andexcess sodium nitrite was consumed by adding 0.3 parts sulfamic acid.Enough sulfamic acid was added until starch iodide paper provided anegative result. 5 parts of the m-toluidine ethoxylate coupler was addedto a flask with 100 mL of water and the temperature lowered to 5 C. Theprepared diazonium salt solution was slowly added into the abovesolution for coupling reaction. Care was taken to not allow thetemperature to rise above 10° C. After complete addition of diazoniumsalt solution, the reaction was allowed to slowly reach room temperatureover an hour. The mixture was then neutralized with sodium hydroxide andphase separated. The product layer was then dissolved with methanol andfiltered to remove any excess salts. The filtrate was evaporated and theproduct of this reaction is ready to use at this point.

Addition of Anhydride to Color Example 1

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofsuccinic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 3

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofsuccinic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 4

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofmaleic anhydride. The reaction is heated to 85° C. for 12 hours and thencooled down to room temperature. The pH of the mixture is adjusted to 7using sodium hydroxide, and the water is removed from the mixture viarotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 5

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofphthalic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 7

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofhexahydrophthalic anhydride. The reaction is heated to 85° C. for 12hours and then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

Example 6

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofallyl succinic anhydride. The reaction is heated to 85° C. for 12 hoursand then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

Example 8

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofoctyl-succinic anhydride. The reaction is heated to 85° C. for 12 hoursand then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

Example 10

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofsuccinic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 11

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofmaleic anhydride. The reaction is heated to 85° C. for 12 hours and thencooled down to room temperature. The pH of the mixture is adjusted to 7using sodium hydroxide, and the water is removed from the mixture viarotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 12

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofphthalic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 14

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofhexahydrophthalic anhydride. The reaction is heated to 85° C. for 12hours and then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

Example 13

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofallyl succinic anhydride. The reaction is heated to 85° C. for 12 hoursand then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

Example 15

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofoctyl-succinic anhydride. The reaction is heated to 85° C. for 12 hoursand then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

Example 17

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofsuccinic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 18

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofmaleic anhydride. The reaction is heated to 85° C. for 12 hours and thencooled down to room temperature. The pH of the mixture is adjusted to 7using sodium hydroxide, and the water is removed from the mixture viarotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 19

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofphthalic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 21

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofhexahydrophthalic anhydride. The reaction is heated to 85° C. for 12hours and then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

Example 24

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofsuccinic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 25

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofmaleic anhydride. The reaction is heated to 85° C. for 12 hours and thencooled down to room temperature. The pH of the mixture is adjusted to 7using sodium hydroxide, and the water is removed from the mixture viarotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 34

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofphthalic anhydride. The reaction is heated to 85° C. for 12 hours andthen cooled down to room temperature. The pH of the mixture is adjustedto 7 using sodium hydroxide, and the water is removed from the mixturevia rotary evaporation. The desired product is obtained in quantitativeconversion as assessed by HPLC.

Example 44

To 25 parts of the thiophene azo polymeric colorant is added 8 parts ofhexahydrophthalic anhydride. The reaction is heated to 85° C. for 12hours and then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

Example 45

To 25 parts of the thiophene azo polymeric colorant is added 16 parts ofhexahydro-phthalic anhydride. The reaction is heated to 85° C. for 12hours and then cooled down to room temperature. The pH of the mixture isadjusted to 7 using sodium hydroxide, and the water is removed from themixture via rotary evaporation. The desired product is obtained inquantitative conversion as assessed by HPLC.

B. Test Methods I. Method for Determining Extinction Coefficient

A sample of 0.1000 grams of color is diluted to volume in a 100 mLvolumetric flask using methanol. 2 mL of this solution are transferredto a second 100 mL volumetric flask and diluted to volume with methanol.The absorbance and lambda max of the diluted colorant are measured usinga spectrophotometer in a 1 cm cell.

Lambda max is taken directly from the spectra

Extinction coefficient=((absorbance/mass used)×5)/MW of colorant

Exemplary Detergent Formulations Formulations 1a-1l Liquid DetergentFormulations

Tables 7A and 7B provide examples of liquid detergent formulations whichinclude at least one thiophene azo dye of the present invention as ahueing agent. The formulations are shown in Table 7A as Formulations 1athrough 1f and in Table 7B as Formulations 1g through 1l.

TABLE 7A Liquid Detergent Formulations Comprising the Inventive HueingAgent 1a 1b 1c 1d 1e 1f ⁵ Ingredient wt % wt % wt % wt % wt % wt %sodium alkyl ether sulfate 14.4%  14.4%  9.2% 5.4% linear alkylbenzenesulfonic 4.4% 4.4% 12.2%  5.7% 1.3% 22.0%  acid alkyl ethoxylate 2.2%2.2% 8.8% 8.1% 3.4% 18.0%  amine oxide 0.7% 0.7% 1.5% citric acid 2.0%2.0% 3.4% 1.9% 1.0% 1.6% fatty acid 3.0% 3.0% 8.3% 16.0%  protease 1.0%1.0% 0.7% 1.0% 2.5% amylase 0.2% 0.2% 0.2% 0.3% lipase 0.2% borax 1.5%1.5% 2.4% 2.9% calcium and sodium formate 0.2% 0.2% formic acid 1.1%amine ethoxylate polymers 1.8% 1.8% 2.1% 3.2% sodium polyacrylate 0.2%sodium polyacrylate 0.6% copolymer DTPA¹ 0.1% 0.1% 0.9% DTPMP² 0.3%EDTA³ 0.1% fluorescent whitening agent 0.15%  0.15%  0.2% 0.12%  0.12% 0.2% ethanol 2.5% 2.5% 1.4% 1.5% propanediol 6.6% 6.6% 4.9% 4.0% 15.7% sorbitol 4.0% ethanolamine 1.5% 1.5% 0.8% 0.1% 11.0%  sodium hydroxide3.0% 3.0% 4.9% 1.9% 1.0% sodium cumene sulfonate 2.0% silicone sudssuppressor 0.01%  perfume 0.3% 0.3% 0.7% 0.3% 0.4% 0.6% Non-tintingdyes⁴ 0.0001%   0.001%  0.008%  0.03%  0.015%  0.05%  Hueing Agent⁶0.01%  0.005%  Hueing Agent⁷ 0.01%  0.02%  0.003%  0.012%  water balancebalance balance balance balance balance 100.0%  100.0%  100.0%  100.0% 100.0%  100.0% 

TABLE 7B Liquid Detergent Formulations Comprising the Inventive HueingAgent 1g 1h 1i 1j 1k 1l⁵ Ingredient wt % wt % wt % wt % wt % wt % sodiumalkyl ether sulfate 14.4%  14.4%  9.2% 5.4% linear lbenzene sulfonicacid 4.4% 4.4% 12.2%  5.7% 1.3% 22.0%  alkyl ethoxylate 2.2% 2.2% 8.8%8.1% 3.4% 18.0%  amine oxide 0.7% 0.7% 1.5% citric acid 2.0% 2.0% 3.4%1.9% 1.0% 1.6% fatty acid 3.0% 3.0% 8.3% 16.0%  protease 1.0% 1.0% 0.7%1.0% 1.7% amylase 0.2% 0.2% 0.2% 0.6% lipase 0.2% 0.2% borax 1.5% 1.5%2.4% 2.9% calcium and sodium formate 0.2% 0.2% formic acid 1.1% amineethoxylate polymers 1.8% 1.8% 2.1% 3.2% sodium polyacrylate 0.2% sodiumpolyacrylate 0.6% copolymer DTPA¹ 0.1% 0.1% 0.9% DTPMP² 0.3% EDTA³ 0.1%fluorescent whitening agent 0.15%  0.15%  0.2% 0.12%  0.12%  0.2%ethanol 2.5% 2.5% 1.4% 1.5% propanediol 6.6% 6.6% 4.9% 4.0% 15.7% sorbitol 4.0% ethanolamine 1.5% 1.5% 0.8% 0.1% 11.0%  sodium hydroxide3.0% 3.0% 4.9% 1.9% 1.0% sodium cumene sulfonate 2.0% silicone sudssuppressor 0.01%  perfume 0.3% 0.3% 0.7% 0.3% 0.4% 0.6% Non-tintingdyes⁴ 0.0001%   0.001%  0.008%  0.03%  0.015%  0.05%  Hueing Agent⁶0.01%  0.005%  Hueing Agent⁷ 0.01%  0.02%  0.003%  0.012%  opacifier⁸0.5% water balance balance balance balance balance balance 100.0% 100.0%  100.0%  100.0%  100.0%  100.0% 

Footnotes for Formulations 1a-l:

¹ diethylenetriaminepentaacetic acid, sodium salt² diethylenetriaminepentakismethylenephosphonic acid, sodium salt³ ethylenediaminetetraacetic acid, sodium salt⁴ a non-tinting dyes used to adjust formula color⁵ compact formula, packaged as a unitized dose in polyvinyl alcohol film⁶ thiophene azo carboxylate hueing agent from Table 6, Examples 1-21,preferably with hueing efficiency >10 and wash removability 30-85%⁷ thiophene azo carboxylate hueing agent from Table 6, Examples 22-48,preferably with hueing efficiency >10 and wash removability 30-85%

⁸ Acusol OP301 Formulations 2a-2e Granular Detergent Formulations

Table 8 provides examples of granular detergent formulations whichinclude at least one thiophene azo carboxylate dye of the presentinvention as a hueing agent. The formulations are shown in Table 8 asFormulations 2a through 2e.

TABLE 8 Granular Detergent Formulations Comprising the Inventive HueingAgent 2a 2b 2c 2d 2e Ingredient wt % wt % wt % wt % wt % Na linearalkylbenzene  3.4%  3.3%  11.0%  3.4%  3.3% sulfonate Na alkylsulfate 4.0%  4.1%  4.0%  4.1% Na alkyl sulfate  9.4%  9.6%  9.4%  9.6%(branched) alkyl ethoxylate  3.5% type A zeolite  37.4%  35.4%  26.8% 37.4%  35.4% sodium carbonate  22.3%  22.5%  35.9%  22.3%  22.5% sodiumsulfate  1.0%  18.8%  1.0% sodium silicate  2.2% protease  0.1%  0.2% 0.1%  0.2% sodium polyacrylate  1.0%  1.2%  0.7%  1.0%  1.2%carboxymethylcellulose  0.1% PEG 600  0.5%  0.5% PEG 4000  2.2%  2.2%DTPA  0.7%  0.6%  0.7%  0.6% fluorescent whitening  0.1%  0.1%  0.1% 0.1%  0.1% agent sodium percarbonate  5.0%  5.0% sodium nonanoyloxyben- 5.3%  5.3% zenesulfonate silicone suds suppressor  0.02%  0.02%  0.02% 0.02% perfume  0.3%  0.3%  0.2%  0.3%  0.3% Hueing Agent¹ 0.004%  0.02%Hueing Agent² 0.006% 0.002% 0.004% water and miscellaneous balancebalance balance balance balance 100.0% 100.0% 100.0% 100.0% 100.0%Footnotes for Formulations 2a-e: ¹thiophene azo carboxylate hueing agentfrom Table 6, Examples 1-21, preferably with hueing efficiency >10 andwash removability 30-85% ²thiophene azo carboxylate hueing agent fromTable 6, Examples 22-48, preferably with hueing efficiency >10 and washremovability 30-85%

Exemplary Fabric Care Compositions Formulations 3a-3d Liquid Fabric CareCompositions

Table 9 provides examples of liquid fabric care compositions whichinclude at least one thiophene azo carboxylate dye of the presentinvention as a hueing agent. The compositions are shown in Table 9 asFormulations 3a through 3d.

TABLE 9 Liquid Fabric Care Compositions Comprising the Inventive HueingAgent Ingredients 3a 3b 3c 3d Fabric Softening Active^(a) 13.70% 13.70%13.70% 13.70% Ethanol  2.14%  2.14%  2.14%  2.14% Cationic Starch^(b) 2.17%  2.17%  2.17%  2.17% Perfume  1.45%  1.45%  1.45%  1.45% PhaseStabilizing Polymer^(c)  0.21%  0.21%  0.21%  0.21% Calcium Chloride0.147% 0.147% 0.147% 0.147% DTPA^(d) 0.007% 0.007% 0.007% 0.007%Preservative^(e)  5 ppm  5 ppm  5 ppm  5 ppm Antifoam^(f) 0.015% 0.015%0.015% 0.015% Hueing Agent.^(g) 30 ppm 15 ppm Hueing Agent^(h) 30 ppmHueing Agent^(i) 30 ppm 15 ppm Tinopal CBS-X^(j) 0.2  0.2  0.2  0.2 Ethoquad C/25^(k) 0.26 0.26 0.26 0.26 Ammonium Chloride  0.1%  0.1% 0.1%  0.1% Hydrochloric Acid 0.012% 0.012% 0.012% 0.012% DeionizedWater Balance Balance Balance Balance Footnotes for Formulations 3a-d:^(a)N,N-di(tallowoyloxyethyl)-N,N-dimethylammonium chloride.^(b)Cationic starch based on common maize starch or potato starch,containing 25% to 95% amylose and a degree of substitution of from 0.02to 0.09, and having a viscosity measured as Water Fluidity having avalue from 50 to 84. ^(c)Copolymer of ethylene oxide and terephthalatehaving the formula described in U.S. Pat. No. 5,574,179 at col.15, lines1-5, wherein each X is methyl, each n is 40, u is 4, each R¹ isessentially 1,4- phenylene moieties, each R² is essentially ethylene,1,2-propylene moieties, or mixtures thereof.^(d)Diethylenetriaminepentaacetic acid. ^(e)KATHON ® CG available fromRohm and Haas Co. ^(f)Silicone antifoam agent available from Dow CorningCorp. under the trade name DC2310. ^(g)thiophene azo carboxylate hueingagent from Table 6, Examples 1-21, preferably with hueing efficiency >10and wash removability 30-85% ^(h)thiophene azo carboxylate hueing agentfrom Table 6, Examples 22-48, preferably with hueing efficiency >10 andwash removability 30-85% ^(i)thiophene azo carboxylate hueing agent fromTable 6, Examples 1-48, preferably with hueing efficiency >10 and washremovability 30-85% ^(j)Disodium 4,4′-bis-(2-sulfostyryl) biphenyl,available from Ciba Specialty Chemicals. ^(k)Cocomethyl ethoxylated [15]ammonium chloride, available from Akzo Nobel.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular aspects of the present invention have been illustratedand described, it would be obvious to those skilled in the art thatvarious other changes and modifications can be made without departingfrom the spirit and scope of the invention. It is therefore intended tocover in the appended claims all such changes and modifications that arewithin the scope of this invention.

We claim:
 1. A laundry care composition comprising: a) a thiophene azocarboxylate dye containing a carboxylic acid moiety, with the provisothat the thiophene azo carboxylate dye does not have the followingstructures

b) a laundry care ingredient.
 2. The laundry care composition of claim1, wherein said thiophene azo carboxylate dye has, in the wavelengthrange of about 400 nm to about 750 nm in methanol solution, a maximumextinction coefficient greater than about 1000 liter/mol/cm.
 3. Thelaundry care composition of claim 2, wherein said thiophene azocarboxylate dye has, in the wavelength range of about 540 nm to about630 nm, a maximum extinction coefficient from about 20,000 to about100,000 liter/mol/cm.
 4. The laundry care composition of claim 3,wherein said thiophene azo carboxylate dye has, in the wavelength rangeof about 560 nm to about 610 nm, a maximum extinction coefficient fromabout 20,000 to about 65,000 liter/mol/cm.
 5. The laundry carecomposition of claim 1, wherein said thiophene azo carboxylate dye has amolecular weight from greater than 232 Daltons, from about 233 Daltonsto about 5000 Daltons, from about 365 Daltons to about 2500 Daltons, oreven from about 423 Daltons to about 1000 Daltons.
 6. The laundry carecomposition of claim 1, wherein said thiophene azo carboxylate dye isrepresented by general Formula (I):

wherein: a.) R₁, R₂ and R₃ are each independently selected fromhydrogen, electron-withdrawing moieties, and electron-donating moieties,provided that at least one of R₁, R₂ and R₃ is an electron-withdrawingmoiety; and b.) wherein X is an organic moiety having a molecular weightfrom about 104 Daltons to about 4871 Daltons, from about 236 Daltons toabout 2371 Daltons from about 294 Daltons to about 871 Daltons.
 7. Thelaundry care composition of claim 6, wherein for said thiophene azocarboxylate dye each R₁, R₂ and R₃ is independently selected fromhydrogen, (C₁-C₄)-alkyl, (C₃-C₁₀)-aryl, carboxylate, cyano, sulfonate,phosphonate, sulfate, acetate, nitro, (C₁-C₄)-alkyl ester, halogen oramino moiety.
 8. The laundry care composition of claim 6, wherein forsaid thiophene azo carboxylate dye X is a moiety having Formula (II)below:

wherein: ii.) R₄ is selected from a moiety having Formula (III) below

wherein: each R₈ is independently selected from hydrogen, C₁-C₈ alkyloptionally substituted with a hydroxy, or acetyl; m is an integer from 0to 10; Y is —OC(O)GCO₂M wherein M is H or a charge balancing cation; Gis an organic group derived from a substituted or unsubstitutedsuccinic, maleic, glutaric, adipic or phthalic anhydride having FormulaIV,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons; ii) R₄ is selected from a moiety having Formula (V)below:

wherein each R₁₁ and R₁₂ is independently selected from hydrogen, C₁-C₈alkyl, aryl, acetyl or hydroxyl moiety; m and n are independent and areintegers from 0 to 10, Y is —OC(O)GCO₂M wherein M is H or a chargebalancing cation; G is an organic group derived from a substituted orunsubstituted succinic, maleic, glutaric, adipic or phthalic anhydridehaving Formula VI,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons; or iii.) R₄ is selected from a moiety having Formula(VII) below:

wherein R₁₃ is selected from a C₆-C₁₀ aryl moiety, C₇-C₁₂ arylalkylmoiety, C₁-C₁₈ alkyl moiety, or a siloxane moiety; each R₁₄ isindependently selected from hydrogen, C₁-C₄ alkyl; m is an integer from0 to 10; Y is —OC(O)GCO₂M wherein M is H or a charge balancing cation; Gis an organic group derived from a substituted or unsubstitutedsuccinic, maleic, glutaric, adipic or phthalic anhydride having FormulaVIII,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons; R₅ is an independently selected R₄ moiety as definedabove or R₅ is selected from C₁-C₁₂ alkyl moiety, a C₂-C₁₂ ether moiety;C₆-C₁₀ aryl moiety or C₇-C₁₂ arylalkyl moiety; wherein the index a is aninteger from 0 to 4, and each R₆ may be independently selected from aC₁-C₆ alkyl, a C₁-C₄ alkoxy, a nitro, a hydroxyl, a halogen, or—NHC(O)R₂₂ wherein R₂₂ is selected from H, —NH₂, C₁-C₆ alkyl, phenyl,—(CH₂)_(s)OR₂₃ where the index s is 1 or 2 and R₂₃ is selected from Me,phenyl, and —CO₂CH₂CN; —NHSO₂R₂₄ wherein R₂₄ is C₁-C₄ alkyl or phenyl;said alkyl, alkoxy and acetamido moieties may be optionally substitutedwith a carboxylate moiety; or, X is a moiety having Formula II above:wherein each R₄ and R₅ can independently be selected from: a)[(CH₂CR′HO)_(x)(CH₂CR″HO)_(y)R₁₅]; b) C₁-C₁₂ alkyl, C₆-C₁₀ aryl orC₇-C₁₂ aryl alkyl; c) [CH₂CH(OR₁₆)CH₂OR₁₇]; d) the amino additionproduct of styrene oxide, glycidyl methyl ether, isobutyl glycidylether, isopropylglycidyl ether, t-butyl glycidyl ether,2-ethylhexylgycidyl ether, and glycidylhexadecyl ether, followed by theaddition of from 1 to 10 alkylene oxide units wherein at least one suchalkyleneoxide unit is substituted with R₁₅ that is not —H; wherein R′ isselected from the group consisting of H, CH₃, CH₂O(CH₂CH₂O)_(z)R₁₅, andmixtures thereof; R″ is selected from the group consisting of H,CH₂O(CH₂CH₂O)_(z)R₁₅, and mixtures thereof; x+y≦20; y≧1; z=0 to 10; eachR₁₅ is independently selected from —H and Y wherein Y is —OC(O)GCO₂Mwherein M is H or a charge balancing cation; G is an organic groupderived from a substituted or unsubstituted succinic, maleic, glutaric,adipic or phthalic anhydride having Formula IX,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons; R₁₆ is selected from the group consisting of H,(CH₂CH₂O)_(z)R₁₅ wherein z=0 to 10, and mixtures thereof; R₁₇ isselected from the group consisting of C₁-C₁₆ alkyl, C₆-C₁₀ aryl groups,and mixtures thereof; the index m is an integer from 0 to 4 and each R₆is as defined above; further provided the molecule contains at least onenon-H R₁₅ group.
 9. The laundry care composition of claim 8, wherein forsaid thiophene azo carboxylate dye X is a moiety having Formula (II)below:

wherein: iv.) R₄ is selected from a moiety having Formula (III) below

wherein: R₈ is a hydrogen, C₁-C₄ alkyl moiety or an C₆-C₁₀ aryl moiety;Y is —OC(O)GCO₂M wherein M is H or a charge balancing cation; G is anorganic group derived from a substituted or unsubstituted succinic,maleic, glutaric, adipic or phthalic anhydride having Formula IV,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons; or, R₄ is selected from a moiety having Formula (V)below:

wherein each R₁₁ and R₁₂ is independently selected from hydrogen, C₁-C₄alkyl or C₆-C₁₀ aryl moiety; m and n are independent and are integersfrom 0 to 5, Y is —OC(O)GCO₂M wherein M is H or a charge balancingcation; G is an organic group derived from a substituted orunsubstituted succinic, maleic, glutaric, adipic or phthalic anhydridehaving Formula VI,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons; or, R₄ is selected from a moiety having Formula (VII)below:

wherein R₁₃ is selected from an C₆-C₁₀ aryl moiety, benzyl moiety, or aC₁-C₁₈ alkyl moiety; each R₁₄ is independently selected from hydrogen or—CH₃; m is an integer from 0 to 10, Y is —OC(O)GCO₂M wherein M is H or acharge balancing cation; G is an organic group derived from asubstituted or unsubstituted succinic, maleic, glutaric, adipic orphthalic anhydride having Formula VIII,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons; ii.) R₅ is an independently selected R₄ moiety asdefined above or R₅ is R₅ selected from C₁-C₆ alkyl moiety or benzylmoiety; v.) wherein the index a is an integer from 0 to 2, and each R₆may be independently selected from methyl, methoxy, or acetamido moiety.10. The laundry care composition of claim 9, wherein for said thiopheneazo carboxylate dye each R₁, R₂ and R₃ is independently selected fromhydrogen, (C₁-C₄)-alkyl, (C₆-C₁₀)-aryl, carboxylate, cyano, sulfonate,acetate, nitro, (C₁-C₄)-alkyl ester, halogen or amino moiety, in oneaspect, each R₁, R₂ and R₃ is independently selected from hydrogen,(C₁-C₄)-alkyl, carboxylate, cyano, sulfonate, nitro, (C₁-C₄)-alkyl esteror halogen moiety.
 11. The laundry care composition of claim 1 whereinsaid thiophene azo carboxylate dye has Formula (X):A-N═N—X  Formula X wherein the A moiety is selected from the groupconsisting of Table 1 A Moieties Nos. 1-118 and wherein X is selectedfrom the group consisting of Table 4 X Moieties Nos. 1-24 wherein G isan organic group derived from a substituted or unsubstituted succinic,maleic, glutaric, adipic or phthalic anhydride having Formula XI,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons.
 12. The laundry care composition of claim 1 whereinsaid thiophene azo carboxylate dye has Formula (XII):A-N═N—X  Formula XII wherein the A moiety is selected from the groupconsisting of Table 1 A Moieties Nos. 9-11, 15, 23, 34-35, 37-39, 41,43, 47, 50-51, 57-58, 77, 83, 89, 95, 106, and 110-118; and wherein theX moiety is selected from the group consisting of Table 4 X MoietiesNos. 1-8, 13, 14, and 18-21, wherein G is an organic group derived froma substituted or unsubstituted succinic, maleic, glutaric, adipic orphthalic anhydride having Formula XIII,

said anhydride having a molecular weight less than about 353 Daltons,from about 98 Daltons to 352 Daltons, or even from about 100 Daltons toabout 325 Daltons.
 13. The laundry care composition of claim 12 whereinsaid G moiety of said thiophene azo carboxylate dye is selected fromTable 5 G Moieties Nos. 1-48.
 14. The laundry care composition of claim1, wherein said thiophene azo carboxylate dye has the following formula:

wherein the moiety A is selected from Table 1 A Moieties Nos. 1-118; a=0to 2; when a=1 or 2, R₆ is selected from Table 2 R₆ Substituent Identityand Position Nos. 1-40; and R₄ and R₅ grouping is selected from Table 3R₄ and R₅ Groupings Nos. 1-83.
 15. The laundry care composition of claim1, wherein said thiophene azo carboxylate dye has the following formula:

wherein the moiety A is selected from Table 1 A Moieties Nos. 9-11, 15,23, 34-35, 37-39, 41, 43, 47, 50-51, 57-58, 77, 83, 89, 95, 106, and110-118; a=0 to 2; when a=1 or 2, R₆ is selected from Table 2 R₆Substituent Identity and Position Nos. 1, 3, 5, 7, 12, 13, 14, 31, 36and 40; and R₄ and R₅ grouping is selected from Table 3 R₄ and R₅Groupings Nos. 3-8, 14, 15, 18-23, 29, 30, 33-38, 44, 45, 48-53, 59, 60,63-66, 71-76, 82 and
 83. 16. The laundry care composition of claim 1,wherein said thiophene azo carboxylate dye has a formula selected fromTable 6 Formula Nos. 1-48, in one aspect, said thiophene azo carboxylatedye has a formula selected from Table 6 Formula Nos. 1-36, 43 and 44.17. The laundry care composition of claim 1, said laundry carecomposition comprising, based on total laundry care composition weight,less than 15% builder, less than 10% builder, or even less than 5%builder.
 18. The laundry care composition of claim 1, said laundry carecomposition being a multi-compartment unit dose product.
 19. The laundrycare composition of claim 1, said laundry care composition comprising,based on total laundry care composition weight, a total of no more than20% water; a total of no more than 15% water; a total of no more than10% water; or even a total of no more than 5% water.
 20. The laundrycare composition of claim 1, said laundry care composition comprising,based on total laundry care composition weight, from about 10% to about70% of a water-miscible organic solvent having a molecular weight ofgreater than 70 Daltons.
 21. The laundry care composition of claim 1,said laundry care composition comprising, based on total laundry carecomposition weight, a perfume microcapsule comprising a core and a shellthat encapsulates said core, said perfume microcapsule having a D[4,3]average particle of from about 0.01 microns to about 200 microns.
 22. Amethod of treating and/or cleaning a surface or fabric comprising thesteps of optionally washing and/or rinsing said surface or fabric,contacting said surface or fabric with a laundry care composition of anyof claims 1-21, then optionally washing and/or rinsing said surfaceand/or fabric then optionally letting said surface or fabric to dryand/or actively drying said surface or fabric.